WO2021132075A1 - Dispersion de composé xanthogène, composition de latex de polymère à base de diène conjugué, corps moulé de film, corps moulé par immersion, et composition d'adhésif - Google Patents

Dispersion de composé xanthogène, composition de latex de polymère à base de diène conjugué, corps moulé de film, corps moulé par immersion, et composition d'adhésif Download PDF

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Publication number
WO2021132075A1
WO2021132075A1 PCT/JP2020/047421 JP2020047421W WO2021132075A1 WO 2021132075 A1 WO2021132075 A1 WO 2021132075A1 JP 2020047421 W JP2020047421 W JP 2020047421W WO 2021132075 A1 WO2021132075 A1 WO 2021132075A1
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conjugated diene
weight
latex
diene polymer
latex composition
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PCT/JP2020/047421
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English (en)
Japanese (ja)
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小出村　順司
実紗 林
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日本ゼオン株式会社
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Publication of WO2021132075A1 publication Critical patent/WO2021132075A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
    • B29C41/14—Dipping a core
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
    • B29C41/34—Component parts, details or accessories; Auxiliary operations
    • B29C41/36—Feeding the material on to the mould, core or other substrate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/06—Sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/38—Thiocarbonic acids; Derivatives thereof, e.g. xanthates ; i.e. compounds containing -X-C(=X)- groups, X being oxygen or sulfur, at least one X being sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00—Compositions of natural rubber
    • C08L7/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/06—Copolymers with styrene
    • C08L9/08—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/10—Latex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J107/00—Adhesives based on natural rubber
    • C09J107/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/06—Copolymers with styrene
    • C09J109/08—Latex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J109/00—Adhesives based on homopolymers or copolymers of conjugated diene hydrocarbons
    • C09J109/10—Latex
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic

Definitions

  • the present invention relates to a xanthogen compound dispersion, a conjugated diene polymer latex composition, a film molded body, a dip molded body, and an adhesive composition, and more specifically, promotes calcification of a polymer such as a conjugated diene polymer.
  • a polymer such as a conjugated diene polymer.
  • a xanthogen compound dispersion capable of making a film polymer such as a body excellent in tensile strength and tear strength, and also excellent in tensile strength and tear strength stability, using such a xantogen compound dispersion.
  • the present invention relates to the obtained conjugated diene polymer latex composition, and a film molded article, a dip molded article, and an adhesive composition comprising such a conjugated diene polymer latex composition.
  • a latex composition containing a latex of natural rubber is dip-molded to obtain a dip-molded body that is used in contact with the human body such as a nipple, a balloon, a glove, a balloon, and a sack.
  • the latex of natural rubber contains a protein that causes the symptoms of immediate allergy (Type I) in the human body, there may be a problem as a dip molded product that comes into direct contact with the living mucosa or organs. Therefore, studies have been conducted on using synthetic rubber latex instead of natural rubber latex.
  • Patent Document 1 discloses a latex composition obtained by blending zinc oxide, sulfur, and a vulcanization accelerator with a latex of synthetic polyisoprene, which is a synthetic rubber, as a composition for dip molding.
  • the technique of Patent Document 1 can prevent the occurrence of immediate allergy (Type I) due to a protein derived from natural rubber, while the vulcanization accelerator contained in the dip molded product when it is used as a dip molded product. When it comes into contact with the human body, it may cause allergic symptoms of delayed type allergy (Type IV).
  • the present invention has been made in view of such an actual situation, and when it is used as a vulcanization accelerator for a polymer such as a conjugated diene polymer and used as a film molded product such as a dip molded product, it is an immediate allergy.
  • a vulcanization accelerator for a polymer such as a conjugated diene polymer
  • a film molded product such as a dip molded product
  • the obtained film polymer such as a dip molded product has excellent tensile strength and tear strength, and has tensile strength.
  • a xanthogen compound dispersion capable of having excellent tear strength stability a conjugated diene polymer latex composition obtained by using such a xanthogen compound dispersion, and such a conjugated diene system. It is an object of the present invention to provide a film molded product, a dip molded product, and an adhesive composition obtained by using a polymer
  • the present inventors have contained a xanthate compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol. It has been found that the xanthate compound dispersion can solve the above-mentioned problems, and based on such findings, the present invention has been completed.
  • a xanthate compound dispersion containing a xanthate compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol.
  • the ratio of the anionic surfactant having no polyoxyalkylene structure to the nonionic surfactant is "anionic surfactant having no polyoxyalkylene structure: nonion".
  • the weight ratio of the "based surfactant” is preferably 99: 1 to 10:90.
  • the anionic surfactant having no polyoxyalkylene structure is preferably an aromatic compound.
  • the number average molecular weight of the nonionic surfactant is preferably 100 to 5,000.
  • a conjugated diene polymer latex composition containing a latex of a conjugated diene polymer, a vulcanizing agent, and the xanthogen compound dispersion of the present invention.
  • the conjugated diene polymer latex composition of the present invention preferably further contains a metal oxide and / or a typical metal compound.
  • the conjugated diene polymer latex composition of the present invention it is preferable that the conjugated diene polymer is a synthetic polyisoprene, a styrene-isoprene-styrene block copolymer, or a natural rubber from which proteins have been removed.
  • a film molded product made of such a conjugated diene polymer latex composition and a film molded product made of such a conjugated diene polymer latex composition, a dip molded product, and an adhesive.
  • the agent composition is provided.
  • a delayed type allergy (Type I) is added to a delayed type allergy (Type I). It is possible to suppress the occurrence of Type IV) symptoms, and the obtained film polymer such as a dip molded product has excellent tensile strength and tear strength, and also has excellent tensile strength and tear strength stability.
  • a xanthogen compound dispersion which can be used, a conjugated diene polymer latex composition obtained by using such a xanthogen compound dispersion, and a film molded product comprising such a conjugated diene polymer latex composition.
  • a dip molded product and an adhesive composition can be provided.
  • the xanthate compound dispersion of the present invention contains a xanthate compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol.
  • the xanthogen compound used in the present invention is a compound that acts as a vulcanization accelerator. Therefore, the xanthogen compound dispersion of the present invention can be suitably used as a vulcanization accelerator for a polymer such as a conjugated diene polymer. it can.
  • the xanthogen compound acts as a vulcanization accelerator during vulcanization, and after vulcanization, it is decomposed into alcohol, carbon disulfide, and the like by the heat applied during vulcanization. In addition, alcohol, carbon disulfide, etc.
  • a vulcanization accelerator for example, a thiuram-based vulcanization accelerator, a dithiocarbamate-based vulcanization accelerator, thiazole
  • Type IV delayed type allergy
  • a system vulcanization accelerator for example, a film such as a dip molded product
  • the xanthogen compound used in the present invention is not particularly limited, and examples thereof include xanthate acid and xanthogenate.
  • R is a linear or branched hydrocarbon
  • Z is a metal atom.
  • X is a number corresponding to the valence of Z, and is usually 1 to 4, preferably 2 to 4, particularly preferably 2.
  • the compound represented by is preferable.
  • the zinc salt of xanthate is more preferable.
  • Dibutylxanthogenates are more preferable, zinc diisopropylxanthogenate and zinc dibutylxanthogenate are further preferable, and zinc diisopropylxanthogenate is particularly preferable.
  • xanthogen compounds may be used alone or in combination of two or more.
  • the xanthate compound used in the present invention is dispersed in the xanthate compound dispersion in the form of particles or powder.
  • the volume average particle size of the xanthogen compound in the xantogen compound dispersion is preferably in the range of 0.001 to 9 ⁇ m, more preferably in the range of 0.05 to 7 ⁇ m, and further preferably in the range of 0.05 to 5 ⁇ m. Particularly preferably, it is in the range of 0.07 to 3 ⁇ m.
  • the xanthogen compound dispersion of the present invention was used as a vulcanization accelerator for a polymer such as a conjugated diene polymer to obtain a film molded product such as a dip molded product.
  • the obtained film-molded article such as a dip-molded article can be made superior in tensile strength and tear strength, and also in stability of tensile strength and tear strength.
  • the 95% volume cumulative diameter (D95) of the xanthate compound in the xanthate compound dispersion is preferably in the range of 0.1 to 43 ⁇ m, more preferably in the range of 0.1 to 40 ⁇ m, and further preferably in the range of 0.1 to 0.1 to 40 ⁇ m. It is in the range of 35 ⁇ m, particularly preferably 0.1 to 20 ⁇ m.
  • the volume average particle diameter and the 95% volume cumulative diameter (D95) of the xantogen compound can be measured using, for example, a laser diffraction / scattering type particle size distribution meter.
  • the content ratio of the xanthate compound in the xanthate compound dispersion of the present invention is preferably 1 to 60% by weight, more preferably 10 to 50% by weight, still more preferably 20 to 20 to the total weight of the xanthate compound dispersion. It is 50% by weight, particularly preferably 30 to 50% by weight.
  • the xanthate compound dispersion of the present invention contains, in addition to the above-mentioned xanthate compound, an anionic surfactant and a nonionic surfactant having no polyoxyalkylene structure, and these are dispersed in water or alcohol. It is a dispersion.
  • the xanthate compound Since the xanthate compound is solid at room temperature and does not dissolve in water or alcohol, it is usually used in a powder state. However, the powdered xanthogen compound tends to have insufficient dispersibility when blended in a latex composition containing a polymer such as a conjugated diene polymer, and therefore, sufficiently exerts its effect as a vulcanization accelerator. There was a problem that it could not be done.
  • a xanthogen compound is used as a vulcanization accelerator, and this is blended with the latex of a polymer such as a conjugated diene polymer to obtain a latex composition, and a film molded product such as a dip molded product is produced.
  • a xanthogen compound is used as a vulcanization accelerator, and this is blended with the latex of a polymer such as a conjugated diene polymer to obtain a latex composition, and a film molded product such as a dip molded product is produced.
  • the same latex composition will be used for several days.
  • the aging (pre-vulcanization) of the latex composition proceeds when several days have passed from the start of use, and therefore, several days from the start of use.
  • the film-molded article obtained by using the latex composition that has passed the above period may have a significantly lower tensile strength and tear strength than the film-molded article obtained immediately after the start of use, and the obtained film-molded article may be significantly reduced. There is a problem that the stability of tensile strength and tear strength (aging stability) of the latex is insufficient.
  • a xanthate compound an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol were used.
  • a dispersion in which the xanthate compound is well dispersed can be obtained, and further, in the state of such a dispersion, the latex of the conjugated diene polymer is mixed with the sulfide. It has been found that a latex composition in which the xanthate compound is well dispersed can be obtained.
  • the obtained film molded product such as a dip molded product can be made excellent in tensile strength and tear strength, and also in stability of tensile strength and tear strength. I found that I could do it.
  • the latex composition is excellent in aging stability, so that even when the latex composition is used for a longer period of time, the tensile strength and the tear strength can be improved. It is possible to produce a film molded product such as a dip molded product without extremely reducing it, and as a result, it contributes to improvement in the production efficiency of the film molded product such as a dip molded product.
  • the anionic surfactant having no polyoxyalkylene structure used in the present invention may be any anionic compound having no polyoxyalkylene structure, and is not particularly limited, but has better dispersibility of the xanthogen compound. From this point of view, aromatic compounds such as aromatic sulfonic acid compounds and aromatic carboxylic acid compounds are preferable, and aromatic sulfonic acid compounds are more preferable.
  • an aromatic sulfonic acid compound represented by the following general formula (1) is preferable.
  • R 1 and R 2 are independently hydrogen atoms or arbitrary organic groups, and M + is a monovalent cation.
  • R 1 and R 2 are mutually. They may be combined to form a ring structure.
  • M + may be any monovalent cation, but are not limited to, H +, alkali metal ions, Ag +, Cu +, NH 4 + are preferable, and alkali metal ions More preferably, Na + and K + are even more preferable, and Na + is particularly preferable.
  • the organic group can be an R 1 and R 2, but not limited to, methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, an isobutyl group , Se-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group and other alkyl groups having 1 to 30 carbon atoms.
  • Cycloalkyl group having 3 to 30 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group and cyclooctyl group; aryl having 6 to 30 carbon atoms such as phenyl group, biphenyl group, naphthyl group and anthranyl group Group; methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, n-pentyloxy group, n-hexyloxy group, phenoxy group, etc.
  • these organic groups may have a substituent, and the position of the substituent can be any position.
  • the ring structure is not particularly limited, but an aromatic compound is preferable, and an aromatic compound having a benzene ring such as benzene or naphthalene is used. More preferably, naphthalene is particularly preferable.
  • these ring structures may have a substituent, and the position of the substituent can be any position.
  • R 1 and R 2 are bonded to each other to form a ring structure.
  • the benzene ring structure is formed in the above general formula (1). More specifically, it is preferable to use a compound having a structure represented by the following general formula (2).
  • R 3 is a divalent hydrocarbon group which may have a substituent, and M + is a monovalent cation.
  • M + may be any monovalent cation, but are not limited to, H +, alkali metal ions, Ag +, Cu +, NH 4 + are preferable, and alkali metal ions More preferably, Na + and K + are even more preferable, and Na + is particularly preferable.
  • R 3 may be a divalent hydrocarbon group which may have a substituent, and is not particularly limited, but an alkylene group having 1 to 10 carbon atoms is preferable, and a methylene group is preferable. Is particularly preferable.
  • the anionic surfactant having no polyoxyalkylene structure preferably has the structure represented by the general formula (2) repeatedly, and the number of repeating units of the structure represented by the general formula (2) is Although not particularly limited, the number is preferably 10 to 100, more preferably 20 to 50.
  • the anionic surfactant having no polyoxyalkylene structure As the anionic surfactant having no polyoxyalkylene structure, the general formula (1) or of an aromatic sulfonic acid compound represented by Formula (2), sulfonate ion group (-SO 3 -) the carboxylic acid ion group (-COO -) was replaced, it is also possible to use an aromatic carboxylic acid compound.
  • R 1 and R 2 in the general formula (1) and R 3 in the general formula (2) are the same as described above.
  • anionic surfactant having no polyoxyalkylene structure used in the present invention is not limited to those described above, and is not limited to those described above, but is limited to sodium laurate, potassium myristate, sodium palmitate, potassium oleate, sodium linolenate, and rosin.
  • Fatty acid salts such as sodium acid acid
  • alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, potassium dodecylbenzene sulfonate, sodium decylbenzene sulfonate, potassium decylbenzene sulfonate, sodium cetylbenzenesulfonate, potassium cetylbenzenesulfonate, etc.
  • Alkyl sulfosuccinates such as sodium (2-ethylhexyl) sulfosuccinate, potassium di (2-ethylhexyl) sulfosuccinate, sodium dioctyl sulfosuccinate
  • alkyl sulphate esters such as sodium lauryl sulfate and potassium lauryl sulfate
  • sodium lauryl phosphate, lauryl Monoalkyl phosphates such as potassium phosphate; etc. can also
  • the weight average molecular weight (Mw) of the anionic surfactant having no polyoxyalkylene structure used in the present invention is preferably 200 to 20000, more preferably 400 to 10000.
  • the number average molecular weight (Mn) of the anionic surfactant having no polyoxyalkylene structure used in the present invention is preferably 100 to 5000, more preferably 200 to 1000.
  • the weight average molecular weight (Mw) and number average molecular weight (Mn) of the anionic surfactant having no polyoxyalkylene structure are values converted to standard polystyrene by gel permeation chromatography analysis.
  • the content of the anionic surfactant having no polyoxyalkylene structure in the xanthate compound dispersion of the present invention is not particularly limited, but is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the xanthate compound. , More preferably 1 to 20 parts by weight, still more preferably 2 to 18 parts by weight, particularly preferably 3 to 15 parts by weight, and most preferably 5 to 10 parts by weight.
  • the nonionic surfactant used in the present invention has a segment in its molecular main chain that acts as a nonionic surfactant.
  • a polyoxyalkylene structure is preferably mentioned as a segment that acts as such a nonionic surfactant.
  • nonionic surfactants include polyoxyalkylene glycol, polyoxyalkylene alkyl ether, polyoxyalkylene alkyl phenyl ether, polyoxyethylene styrene phenyl ether, polyoxyethylene (hardened) castor oil, and polyoxyethylene alkyl.
  • examples include amines and fatty acid alkanolamides.
  • polyoxyalkylene glycol examples include polyoxypropylene glycol ethylene oxide adducts such as polyoxyethylene glycol, polyoxypropylene glycol, and polyoxyethylene polyoxypropylene glycol.
  • polyoxyalkylene alkyl ether examples include linear or branched chain ethers to which 1 to 50 (preferably 1 to 10) propylene oxide and / or ethylene oxide are added.
  • Examples include chain-shaped or branched-chain ethers, and linear or branched-chain ethers in which a total of 2 to 50 (preferably 2 to 10) blocks of ethylene oxide and propylene oxide are added or randomly added.
  • polyoxyalkylene alkyl ether examples include polyoxyethylene oleyl ether, polyoxyethylene octyldodecyl ether, polyoxyethylene dodecyl ether, polyoxyethylene lauryl ether, and the like, among these, polyoxyethylene oleyl ether and polyoxy. Polyethylene octyldodecyl ether is preferred.
  • polyoxyalkylene alkyl phenyl ether examples include compounds in which 1 to 50 (preferably 1 to 10) of propylene oxide and / or ethylene oxide are added to the alkyl phenol.
  • polyoxyethylene styrene phenyl ether examples include ethylene oxide adducts of (mono, di, tri) styrene phenol, and among these, polyoxyethylene di, which is an ethylene oxide adduct of distyrene phenol. Polyethylene phenyl ether is preferred.
  • polyoxyethylene (hardened) castor oil examples include castor oil and ethylene oxide adducts of hardened castor oil.
  • fatty acid alkanolamide examples include lauric acid diethanolamide, palmitic acid diethanolamide, myristic acid diethanolamide, stearic acid diethanolamide, oleic acid diethanolamide, palm oil fatty acid diethanolamide, and coconut oil fatty acid diethanolamide.
  • nonionic surfactants a nonionic surfactant having a polyoxyalkylene structure is preferable, a nonionic surfactant having a polyoxyethylene structure is more preferable, and a hydrocarbylated ether of polyoxyethylene is more preferable.
  • Polyoxyethylene alkyl ethers and polyoxyethylene distyrene phenyl ethers are more preferred, and polyoxyethylene alkyl ethers are particularly preferred.
  • the nonionic surfactant may be used alone or in combination of two or more.
  • the nonionic surfactant used in the present invention is a nonionic anionic surfactant having a segment acting as an anionic surfactant in addition to a segment acting as a nonionic surfactant. There may be.
  • the nonionic surfactant used in the present invention preferably does not have a segment that acts as an anionic surfactant.
  • nonionic anionic surfactant examples include compounds represented by the following general formula (3).
  • R 4- O- (CR 5 R 6 CR 7 R 8 ) n- SO 3 M (3)
  • R 4 is an aryl group having 6 to 14 carbon atoms which may be substituted with an alkyl group having 6 to 16 carbon atoms or an alkyl group having 1 to 25 carbon atoms
  • R 5 to R 8 is a group independently selected from the group consisting of hydrogen and methyl groups
  • M is an alkali metal atom or ammonium ion
  • n is 3 to 40.
  • Specific examples of the compound represented by the above general formula (3) include polyoxyethylene lauryl ether sulfate, polyoxyethylene cetyl ether sulfate, polyoxyethylene stearyl ether sulfate, polyoxyethylene oleyl ether sulfate, and the like.
  • nonionic anionic surfactants the nonionic anionic surfactant having a polyoxyalkylene structure is preferable, and the nonionic anionic surfactant having a polyoxyethylene structure is more preferable.
  • the nonionic anionic surfactant may be used alone or in combination of two or more.
  • the number average molecular weight (Mn) of the nonionic surfactant used in the present invention is preferably 100 to 5000, more preferably 150 to 3500, still more preferably 180 to 2500, and particularly preferably 200 to 1000.
  • the number average molecular weight of the nonionic surfactant is, for example, a measurement sample obtained by dissolving the nonionic surfactant in tetrahydrofuran to prepare a 0.2 wt% solution and then filtering with a 0.45 ⁇ m membrane filter. It can be determined as a standard polystyrene-equivalent number average molecular weight by measuring under the following conditions using gel permeation chromatography (GPC).
  • Measuring device HLC-8220GPC (manufactured by Tosoh) Column: TSKgel G1000H (manufactured by Tosoh), TSKgel G2000H (manufactured by Tosoh) Eluent: tetrahydrofuran (THF) Elution rate: 0.3 ml / min Detector: RI (polarity (+)) Column temperature: 40 ° C
  • the content of the nonionic surfactant in the xanthogen compound dispersion of the present invention is not particularly limited, but is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight, based on 100 parts by weight of the xanthogen compound. It is by weight, more preferably 1.2 to 15 parts by weight, particularly preferably 1.5 to 10 parts by weight, and most preferably 2 to 5 parts by weight.
  • the ratio of the anionic surfactant having no polyoxyalkylene structure to the nonionic surfactant in the xanthogen compound dispersion of the present invention is "anionic surfactant having no polyoxyalkylene structure: nonionic.
  • the weight ratio of the "surfactant” is preferably 99: 1 to 10:90, more preferably 97: 3 to 15:85, and even more preferably 95: 5 to 55:45. , 90:10 to 55:45, most preferably 85:15 to 70:30.
  • the water or alcohol used in the present invention is preferably at least one selected from water, methanol, ethanol, propanol and butanol, and more preferably water. That is, the xanthate compound dispersion of the present invention is preferably an aqueous dispersion.
  • an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, water or an alcohol are mixed, and then the obtained mixed solution is used.
  • a method of performing a crushing treatment is preferable.
  • the crushing treatment may be any treatment that can alleviate the crushing and aggregation of the xanthate compound contained in the dispersion, and is not particularly limited, but for example, shearing action or grinding. Examples thereof include a method using a known crusher, such as a method using a crusher utilizing the action and a method using a stirring type crusher.
  • a crushing device such as a roll mill, a hammer mill, a vibration mill, a jet mill, a ball mill, a planetary ball mill, a bead mill, a sand mill, or a three-roll mill can be used.
  • a method of performing the crushing treatment using a ball mill, a planetary ball mill, or a bead mill is preferable.
  • a medium having a media size of preferably ⁇ 5 to ⁇ 50 mm, more preferably ⁇ 10 to ⁇ 35 mm is used, and the rotation speed is preferably 10 to 300 rpm. It is preferable to carry out the crushing treatment under the conditions of more preferably 10 to 100 rpm and a treatment time of preferably 24 to 120 hours, more preferably 24 to 72 hours.
  • a medium having a media size of preferably ⁇ 0.1 to ⁇ 5 mm, more preferably ⁇ 0.3 to ⁇ 3 mm is used, and the rotation speed is high.
  • the crushing treatment is preferably carried out under the conditions of preferably 100 to 1000 rpm, more preferably 100 to 500 rpm, and a treatment time of preferably 0.25 to 5 hours, more preferably 0.25 to 3 hours. is there. Further, when the crushing treatment is performed using a bead mill, a medium having a media size of preferably ⁇ 0.1 to ⁇ 3 mm, more preferably ⁇ 0.1 to ⁇ 1 mm is used, and the rotation speed is preferably high. Is preferably 1000 to 10000 rpm, more preferably 1000 to 5000 rpm, and the treatment time is preferably 0.25 to 5 hours, more preferably 0.25 to 3 hours.
  • the conjugated diene polymer latex composition of the present invention contains the latex of the conjugated diene polymer, a vulcanizing agent, and the above-mentioned xanthogen compound dispersion of the present invention.
  • the conjugated diene polymer constituting the latex of the conjugated diene polymer is not particularly limited, and for example, synthetic polyisoprene, styrene-isoprene-styrene block copolymer (SIS), natural rubber from which proteins have been removed, and nitrile.
  • examples thereof include group-containing conjugated diene-based copolymers. Among these, those containing isoprene units such as synthetic polyisoprene, SIS, and natural rubber from which proteins have been removed are preferable, and synthetic polyisoprene is particularly preferable.
  • the conjugated diene polymer may be an acid-modified conjugated diene polymer obtained by modifying with a monomer having an acidic group.
  • the synthetic polyisoprene may be a homopolymer of isoprene, or may be a copolymer of isoprene and another ethylenically unsaturated monomer copolymerizable with isoprene. It may be a polymer.
  • the content of the isoprene unit in the synthetic polyisoprene is preferably 70% by weight or more with respect to all the monomer units because it is easy to obtain a film molded product such as a dip molded product which is flexible and has excellent tensile strength. It is more preferably 90% by weight or more, further preferably 95% by weight or more, and particularly preferably 100% by weight (a homopolymer of isoprene).
  • ethylenically unsaturated monomers copolymerizable with isoprene include conjugated diene monomers other than isoprene such as butadiene, chloroprene, 1,3-pentadiene; acrylonitrile, methacrylonitrile, fumaronitrile, ⁇ -.
  • Ethylene unsaturated nitrile monomers such as chloroacrylonitrile; vinyl aromatic monomers such as styrene and alkylstyrene; methyl (meth) acrylate (meaning "methyl acrylate and / or methyl methacrylate” and below.
  • Synthetic polyisoprene is prepared in an inert polymerization solvent using a conventionally known method, for example, a Cheegler-based polymerization catalyst composed of trialkylaluminum-titanium tetrachloride or an alkyllithium polymerization catalyst such as n-butyllithium or sec-butyllithium.
  • a Cheegler-based polymerization catalyst composed of trialkylaluminum-titanium tetrachloride or an alkyllithium polymerization catalyst such as n-butyllithium or sec-butyllithium.
  • Isoprene and other copolymerizable ethylenically unsaturated monomers used as needed can be obtained by solution polymerization.
  • the polymer solution of synthetic polyisoprene obtained by solution polymerization may be used as it is for the production of synthetic polyisoprene latex, but after taking out solid synthetic polyisoprene from the polymer solution, it is dissolved in an organic solvent. It can also be used in the production of synthetic polyisoprene latex. Further, when a polymer solution of synthetic polyisoprene is obtained by the above-mentioned method, impurities such as the residue of the polymerization catalyst remaining in the polymer solution may be removed. Further, an anti-aging agent described later may be added to the solution during or after the polymerization. Alternatively, a commercially available solid synthetic polyisoprene can be used.
  • the content ratio of the cis bond unit in the isoprene unit contained in the synthetic polyisoprene is preferably 70% by weight or more with respect to the total isoprene unit. It is more preferably 90% by weight or more, still more preferably 95% by weight or more.
  • the weight average molecular weight of the synthetic polyisoprene is preferably 10,000 to 5,000,000, more preferably 500,000 to 5,000,000, more preferably 500,000 to 5,000,000, in terms of standard polystyrene by gel permeation chromatography analysis. Is between 800,000 and 3,000,000.
  • the polymer Mooney viscosity (ML1 + 4, 100 ° C.) of the synthetic polyisoprene is preferably 50 to 85, more preferably 60 to 85, and even more preferably 70 to 85.
  • a solution or a fine suspension of synthetic polyisoprene dissolved or finely dispersed in an organic solvent is emulsified in water in the presence of an anionic surfactant. Then, if necessary, a method for producing a synthetic polyisoprene latex by removing an organic solvent, (2) isoprene alone or a mixture of isoprene and an ethylenically unsaturated monomer copolymerizable therewith, anionic surface activity.
  • a method of directly producing a synthetic polyisoprene latex by emulsification polymerization or suspension polymerization in the presence of an agent can be mentioned, but synthetic polyisoprene having a high ratio of cis-bonding units in isoprene units can be used.
  • the production method (1) above is preferable from the viewpoint that a film-formed body such as a dip-formed body having excellent mechanical properties such as tensile strength can be easily obtained.
  • Examples of the organic solvent used in the production method (1) above include aromatic hydrocarbon solvents such as benzene, toluene and xylene; alicyclic hydrocarbon solvents such as cyclopentane, cyclopentene, cyclohexane and cyclohexene; pentane, hexane and the like.
  • An aliphatic hydrocarbon solvent such as heptane; a halogenated hydrocarbon solvent such as methylene chloride, chloroform and ethylene dichloride; and the like can be mentioned.
  • an alicyclic hydrocarbon solvent is preferable, and cyclohexane is particularly preferable.
  • the amount of the organic solvent used is preferably 2,000 parts by weight or less, more preferably 20 to 1,500 parts by weight, and further preferably 500 to 1,500 parts by weight with respect to 100 parts by weight of the synthetic polyisoprene.
  • anionic surfactant used in the production method (1) above examples include fatty acid salts such as sodium laurate, potassium myristate, sodium palmitate, potassium oleate, sodium linolenate, and sodium loginate; dodecylbenzene sulfonate.
  • Alkylbenzene sulfonates such as sodium acid, potassium dodecylbenzene sulfonate, sodium decylbenzene sulfonate, potassium decylbenzene sulfonate, sodium cetylbenzenesulfonate, potassium cetylbenzenesulfonate; sodium di (2-ethylhexyl) sulfosuccinate, di (2-Ethylhexyl) Alkyl sulfosuccinates such as potassium sulfosuccinate and sodium dioctyl sulfosuccinate; alkyl sulfates such as sodium lauryl sulfate and potassium lauryl sulfate; sodium polyoxyethylene lauryl ether sulfate, potassium polyoxyethylene lauryl ether sulfate, etc. Polyoxyethylene alkyl ether sulfate ester salt; monoalkyl phosphate such as sodium lau
  • fatty acid salts, alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfates and polyoxyethylene alkyl ether sulfates are preferable, and fatty acid salts and alkylbenzene sulfonates are particularly preferable.
  • a trace amount of the polymerization catalyst (particularly aluminum and fatty acid) derived from synthetic polyisoprene can be removed more efficiently, and the generation of agglomerates in the production of the conjugated diene polymer latex composition is suppressed. Therefore, it is preferable to use at least one selected from the group consisting of alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfates and polyoxyethylene alkyl ether sulfates in combination with fatty acid salts. It is particularly preferable to use the alkylbenzene sulfonate in combination with the fatty acid salt.
  • fatty acid salt sodium loginate and potassium loginate are preferable, and as the alkylbenzene sulfonate, sodium dodecylbenzene sulfonate and potassium dodecylbenzene sulfonate are preferable.
  • these surfactants may be used alone or in combination of two or more.
  • At least one selected from the group consisting of alkylbenzene sulfonates, alkylsulfosuccinates, alkylsulfate salts and polyoxyethylene alkylether sulfates should be used in combination with fatty acid salts.
  • the resulting latex contains at least one selected from alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfates and polyoxyethylene alkyl ether sulfates, and fatty acid salts. ..
  • a surfactant other than the anionic surfactant may be used in combination, and the surfactant other than the anionic surfactant may be ⁇ , ⁇ -non.
  • examples thereof include copolymerizable surfactants such as sulfoesters of saturated carboxylic acids, sulfate esters of ⁇ , ⁇ -unsaturated carboxylic acids, and sulfoalkylaryl ethers.
  • the amount of the anionic surfactant used in the production method (1) is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, based on 100 parts by weight of the synthetic polyisoprene. is there.
  • the total amount of these surfactants used is in the above range. That is, for example, when at least one selected from alkylbenzene sulfonate, alkylsulfosuccinate, alkylsulfate ester salt and polyoxyethylene alkyl ether sulfate ester salt is used in combination with a fatty acid salt, these It is preferable that the total amount used is in the above range. If the amount of anionic surfactant used is too small, a large amount of agglomerates may be generated during emulsification. May occur.
  • alkylbenzene sulfonate, alkylsulfosuccinate, alkyl sulfate ester salt and polyoxyethylene alkyl ether sulfate ester salt is used in combination as an anionic surfactant
  • a fatty acid salt is used in combination.
  • the ratio of these to be used is "fatty acid salt”: "alkylbenzene sulfonate, alkyl sulfosuccinate, alkyl sulfate ester salt and polyoxyethylene alkyl ether sulfate ester salt".
  • the weight ratio of "total of agents” is preferably in the range of 1: 1 to 10: 1, and more preferably in the range of 1: 1 to 7: 1. Too much of the surfactant selected from alkylbenzene sulfonates, alkyl sulfosuccinates, alkyl sulfates and polyoxyethylene alkyl ether sulfates will result in the handling of synthetic polyisoprenes. Foaming may become intense, which requires operations such as standing for a long time and adding an antifoaming agent, which may lead to deterioration of workability and cost increase.
  • the amount of water used in the production method (1) is preferably 10 to 1,000 parts by weight, more preferably 30 to 500 parts by weight, most preferably 30 parts by weight, based on 100 parts by weight of the organic solvent solution of synthetic polyisoprene. Is 50 to 100 parts by weight.
  • Examples of the type of water used include hard water, soft water, ion-exchanged water, distilled water, zeolite water and the like, and soft water, ion-exchanged water and distilled water are preferable.
  • the method of adding the anionic surfactant to the synthetic polyisoprene solution or microsuspension is not particularly limited, and it is previously added to water, the synthetic polyisoprene solution or the fine suspension, or both. It may be added, may be added to the emulsified solution during the emulsification operation, may be added all at once, or may be added in portions.
  • emulsifying device examples include batch emulsification such as the product name "homogenizer” (manufactured by IKA), the product name “Polytron” (manufactured by Kinematica), and the product name “TK autohomo mixer” (manufactured by Tokushu Kagaku Kogyo Co., Ltd.).
  • Membrane emulsifiers such as the product name "Membrane Emulsifier” (manufactured by Refrigeration Industry Co., Ltd.); Vibration type emulsifiers such as the product name "Vibro Mixer” (manufactured by Refrigeration Industry Co., Ltd.); Product name “Ultrasonic Homogenizer” (Branson) Ultrasonic emulsifiers such as (manufactured by the company); etc.
  • the conditions for the emulsification operation by the emulsification device are not particularly limited, and the treatment temperature, treatment time, and the like may be appropriately selected so as to obtain a desired dispersed state.
  • the organic solvent from the emulsion obtained through the emulsification operation.
  • a method for removing the organic solvent from the emulsion a method in which the content of the organic solvent (preferably alicyclic hydrocarbon solvent) in the obtained synthetic polyisoprene latex can be 500% by weight ppm or less is preferable.
  • methods such as vacuum distillation, atmospheric distillation, steam distillation, and centrifugation can be adopted.
  • the total content of the alicyclic hydrocarbon solvent and the aromatic hydrocarbon solvent as the organic solvent in the obtained synthetic polyisoprene latex can be 500% by weight ppm or less.
  • Such a method is not particularly limited, and methods such as vacuum distillation, atmospheric distillation, steam distillation, and centrifugation can be adopted.
  • a concentration operation may be performed by a method such as vacuum distillation, atmospheric distillation, centrifugation, or membrane concentration.
  • a method such as vacuum distillation, atmospheric distillation, centrifugation, or membrane concentration.
  • centrifugation it is preferable to carry out centrifugation from the viewpoint that the solid content concentration of the synthetic polyisoprene latex can be increased and the residual amount of the surfactant in the synthetic polyisoprene latex can be reduced.
  • Centrifugation uses, for example, a continuous centrifuge to centrifuge the centrifugal force, preferably 100 to 10,000 G, and the solid content concentration of the synthetic polyisoprene latex before centrifugation, preferably 2 to 15% by weight.
  • the flow velocity to be sent to the machine is preferably 500 to 1700 kg / hr, and the back pressure (gauge pressure) of the centrifuge is preferably -0.05 to 1.6 MPa, more preferably 0.03 to 1.6 MPa.
  • Synthetic polyisoprene latex can be obtained as a light liquid after centrifugation. As a result, the residual amount of the surfactant in the synthetic polyisoprene latex can be reduced.
  • the solid content concentration of the synthetic polyisoprene latex is preferably 30 to 70% by weight, more preferably 40 to 70% by weight. If the solid content concentration is too low, the solid content concentration of the conjugated diene-based polymer latex composition becomes low, so that the film-formed body such as the obtained dip-molded body becomes thin and easily torn. On the other hand, if the solid content concentration is too high, the viscosity of the synthetic polyisoprene latex becomes high, which may make it difficult to transfer the synthetic polyisoprene latex or stir it in the compounding tank.
  • the volume average particle size of the synthetic polyisoprene latex is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 3 ⁇ m, and even more preferably 0.5 to 2.0 ⁇ m.
  • synthetic polyisoprene latex contains additives such as pH adjusters, defoamers, preservatives, cross-linking agents, chelating agents, oxygen scavengers, dispersants, and anti-aging agents, which are usually blended in the field of latex. May be blended.
  • the pH adjuster include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium hydrogen carbonate; ammonia. ; Organic amine compounds such as trimethylamine and triethanolamine; etc., but alkali metal hydroxides or ammonia are preferable.
  • SIS styrene-isoprene-styrene block copolymer
  • SIS can be obtained by block copolymerization of isoprene and styrene in an inert polymerization solvent using a conventionally known method, for example, an active organometallic such as n-butyllithium as an initiator.
  • the obtained SIS polymer solution may be used as it is in the production of SIS latex, but after taking out the solid SIS from the polymer solution, the solid SIS is dissolved in an organic solvent to SIS. It can also be used in the production of latex.
  • the method for producing SIS latex is not particularly limited, but a SIS solution or fine suspension dissolved or finely dispersed in an organic solvent is emulsified in water in the presence of a surfactant, and the organic solvent is removed if necessary.
  • the method for producing the SIS latex is preferable. At this time, impurities such as the residue of the polymerization catalyst remaining in the polymer solution after the synthesis may be removed. Further, an anti-aging agent described later may be added to the solution during or after the polymerization. Alternatively, a commercially available solid SIS can be used.
  • the organic solvent the same solvent as in the case of the synthetic polyisoprene can be used, and aromatic hydrocarbon solvents and alicyclic hydrocarbon solvents are preferable, and cyclohexane and toluene are particularly preferable.
  • the amount of the organic solvent used is usually 50 to 2,000 parts by weight, preferably 80 to 1,000 parts by weight, more preferably 100 to 500 parts by weight, still more preferably 150 to 300 parts by weight, based on 100 parts by weight of SIS. It is a part by weight.
  • anionic surfactant is preferable, and sodium loginate and sodium dodecylbenzenesulfonate are particularly preferable.
  • the amount of the surfactant used is preferably 0.1 to 50 parts by weight, more preferably 0.5 to 30 parts by weight, based on 100 parts by weight of SIS. If this amount is too small, the stability of the latex tends to be poor, and conversely, if it is too large, foaming tends to occur, which may cause problems during dip molding.
  • the amount of water used in the above-mentioned method for producing SIS latex is preferably 10 to 1,000 parts by weight, more preferably 30 to 500 parts by weight, and most preferably 50 parts by weight with respect to 100 parts by weight of the organic solvent solution of SIS. ⁇ 100.
  • Examples of the type of water used include hard water, soft water, ion-exchanged water, distilled water, and zeolite water. Further, a polar solvent typified by alcohol such as methanol may be used in combination with water.
  • the same method as in the case of the above synthetic polyisoprene can be exemplified.
  • an apparatus for emulsifying an organic solvent solution or a fine suspension of SIS in water in the presence of a surfactant can be exemplified as the same as in the case of the synthetic polyisoprene described above.
  • the method of adding the surfactant is not particularly limited, and the surfactant may be added to water, an organic solvent solution of SIS, a fine suspension, or both in advance, or during the emulsification operation. In addition, it may be added to the emulsion, may be added all at once, or may be added separately.
  • the organic solvent from the emulsion obtained through the emulsification operation it is preferable to remove the organic solvent from the emulsion obtained through the emulsification operation to obtain SIS latex.
  • the method for removing the organic solvent from the emulsion is not particularly limited, and methods such as vacuum distillation, atmospheric distillation, steam distillation, and centrifugation can be adopted.
  • a concentration operation may be performed by a method such as vacuum distillation, atmospheric distillation, centrifugation, or membrane concentration.
  • the solid content concentration of the SIS latex is preferably 30 to 70% by weight, more preferably 50 to 70% by weight. If the solid content concentration is too low, the solid content concentration of the conjugated diene-based polymer latex composition becomes low, so that when a film molded product such as a dip molded product is formed, the film thickness becomes thin and it becomes easy to tear. On the contrary, if the solid content concentration is too high, the viscosity of the SIS latex becomes high, and it becomes difficult to transfer the SIS latex by piping or to stir it in the compounding tank.
  • SIS latex contains additives such as pH adjusters, antifoaming agents, preservatives, cross-linking agents, chelating agents, oxygen scavengers, dispersants, and anti-aging agents, which are usually blended in the field of latex. You may.
  • pH adjuster the same as in the case of the above synthetic polyisoprene can be exemplified, and alkali metal hydroxide or ammonia is preferable.
  • the content of the styrene unit in the styrene block in the SIS contained in the SIS latex thus obtained is preferably 70 to 100% by weight, more preferably 90 to 100% by weight, based on all the monomer units. , More preferably 100% by weight.
  • the content of the isoprene unit in the isoprene block in SIS is preferably 70 to 100% by weight, more preferably 90 to 100% by weight, still more preferably 100% by weight, based on all the monomer units.
  • the content ratio of the styrene unit and the isoprene unit in the SIS is a weight ratio of "styrene unit: isoprene unit", which is usually 1:99 to 90:10, preferably 3:97 to 70:30, and more preferably 5. : 95 to 50:50, more preferably 10:90 to 30:70.
  • the weight average molecular weight of SIS is preferably 10,000 to 1,000,000, more preferably 50,000 to 500,000, still more preferably 100,000 in terms of standard polystyrene by gel permeation chromatography analysis. ⁇ 300,000.
  • the volume average particle size of the latex particles (SIS particles) in the SIS latex is preferably 0.1 to 10 ⁇ m, more preferably 0.5 to 3 ⁇ m, and even more preferably 0.5 to 2.0 ⁇ m.
  • natural rubber from which proteins have been removed can also be used.
  • natural rubber contained in latex obtained from a natural rubber tree and natural rubber contained in latex treated with the latex can be used, for example.
  • Natural rubber contained in field latex collected from a natural rubber tree, natural rubber contained in commercially available natural rubber latex obtained by treating field latex with ammonia or the like can be used.
  • the method for removing the protein from the natural rubber in obtaining the natural rubber from which the protein has been removed is not particularly limited, but the natural rubber latex is reacted with a urea compound in the presence of a surfactant to obtain the natural rubber. After denaturing the protein contained therein, the natural rubber latex containing such a modified protein is subjected to treatments such as centrifugation, coagulation of rubber content, and ultrafiltration to obtain the natural rubber and the modified protein. By separating and removing this denatured protein, a natural rubber latex from which the protein has been removed can be obtained.
  • conjugated diene-based polymer as described above, a nitrile group-containing conjugated diene-based copolymer can also be used.
  • the nitrile group-containing conjugated diene-based copolymer is a copolymer obtained by copolymerizing an ethylenically unsaturated nitrile monomer with a conjugated diene monomer, and in addition to these, these are used as needed. It may be a copolymer obtained by copolymerizing another ethylenically unsaturated monomer copolymerizable with.
  • conjugated diene monomer examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene and chloroprene. Be done. Among these, 1,3-butadiene and isoprene are preferable, and 1,3-butadiene is more preferable.
  • These conjugated diene monomers can be used alone or in combination of two or more.
  • the content ratio of the conjugated diene monomer unit formed by the conjugated diene monomer in the nitrile group-containing conjugated diene-based copolymer is preferably 56 to 78% by weight, more preferably 56 to 73% by weight. , More preferably 56 to 68% by weight. By setting the content of the conjugated diene monomer unit in the above range, the obtained film molded product such as a dip molded product can be made excellent in texture and elongation.
  • the ethylenically unsaturated nitrile monomer is not particularly limited as long as it is an ethylenically unsaturated monomer containing a nitrile group, and for example, acrylonitrile, methacrylonitrile, fumaronitrile, ⁇ -chloroacrylonitrile, ⁇ -cyanoethylacrylonitrile. And so on. Of these, acrylonitrile and methacrylonitrile are preferable, and acrylonitrile is more preferable. These ethylenically unsaturated nitrile monomers can be used alone or in combination of two or more.
  • the content ratio of the ethylenically unsaturated nitrile monomer unit formed of the ethylenically unsaturated nitrile monomer in the nitrile group-containing conjugated diene copolymer is preferably 20 to 40% by weight, more preferably 20 to 40% by weight. Is 25 to 40% by weight, more preferably 30 to 40% by weight.
  • ethylenically unsaturated monomers copolymerizable with the conjugated diene monomer and the ethylenically unsaturated nitrile monomer include, for example, ethylenically unsaturated, which is an ethylenically unsaturated monomer containing a carboxyl group.
  • Saturated carboxylic acid monomer Vinyl aromatic monomer such as styrene, alkylstyrene, vinylnaphthalene; Fluoroalkylvinyl ether such as fluoroethyl vinyl ether; (meth) acrylamide, N-methylol (meth) acrylamide, N, N-dimethylol Ethylene unsaturated amide monomers such as (meth) acrylamide, N-methoxymethyl (meth) acrylamide, N-propoxymethyl (meth) acrylamide; methyl (meth) acrylate, ethyl (meth) acrylate, (meth) Butyl acrylate, -2-ethylhexyl (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, dibutyl maleate, dibutyl fumarate, diethyl maleate, methoxy (me
  • Crosslinkable monomer and the like.
  • These ethylenically unsaturated monomers can be used alone or in combination of two or more.
  • an ethylenically unsaturated carboxylic acid monomer as another copolymerizable ethylenically unsaturated monomer, the nitrile group-containing conjugated diene copolymer is provided with a carboxyl group. be able to.
  • the ethylenically unsaturated carboxylic acid monomer is not particularly limited as long as it is an ethylenically unsaturated monomer containing a carboxyl group, but for example, a single amount of an ethylenically unsaturated monocarboxylic acid such as acrylic acid or methacrylic acid.
  • Esterically unsaturated polycarboxylic acid monomer such as itaconic acid, maleic acid, fumaric acid; ethylenically unsaturated polycarboxylic acid anhydride such as maleic anhydride, citraconic anhydride; monobutyl fumarate, maleic acid
  • ethylenically unsaturated polycarboxylic acid partial ester monomers such as monobutyl and mono-2-hydroxypropyl maleate.
  • ethylenically unsaturated monocarboxylic acid is preferable, and methacrylic acid is particularly preferable.
  • These ethylenically unsaturated carboxylic acid monomers can also be used as alkali metal salts or ammonium salts.
  • the ethylenically unsaturated carboxylic acid monomer can be used alone or in combination of two or more.
  • the content ratio of the ethylenically unsaturated carboxylic acid monomer unit formed by the ethylenically unsaturated carboxylic acid monomer in the nitrile group-containing conjugated diene-based copolymer is preferably 2 to 5% by weight. It is more preferably 2 to 4.5% by weight, still more preferably 2.5 to 4.5% by weight.
  • the content ratio of the other monomer unit formed by the other ethylenically unsaturated monomer in the nitrile group-containing conjugated diene-based copolymer is preferably 10% by weight or less, more preferably 5% by weight. % Or less, more preferably 3% by weight or less.
  • the nitrile group-containing conjugated diene-based copolymer can be obtained by copolymerizing a monomer mixture containing the above-mentioned monomer, and a method of copolymerizing by emulsion polymerization is preferable.
  • a method of copolymerizing by emulsion polymerization is preferable.
  • the emulsion polymerization method a conventionally known method can be adopted.
  • the number average particle size of the latex of the nitrile group-containing conjugated diene copolymer is preferably 60 to 300 nm, more preferably 80 to 150 nm.
  • the particle size can be adjusted to a desired value by a method such as adjusting the amount of the emulsifier and the polymerization initiator used.
  • conjugated diene-based polymer used in the present invention as described above, synthetic polyisoprene, styrene-isoprene-styrene block copolymer (SIS), natural rubber from which proteins have been removed, and nitrile group-containing conjugated diene-based polymer are used.
  • SIS styrene-isoprene-styrene block copolymer
  • Polymers and the like can be used, but the present invention is not limited to these, and butadiene polymers, styrene-butadiene copolymers and the like may be used.
  • the butadiene polymer may be a homopolymer of 1,3-butadiene as a conjugated diene monomer, or another ethylenically non-polymerizable copolymer with 1,3-butadiene as a conjugated diene monomer. It may be a copolymer obtained by copolymerizing with a saturated monomer.
  • the styrene-butadiene copolymer is a copolymer obtained by copolymerizing 1,3-butadiene as a conjugated diene monomer with styrene, and in addition to these, it is used as needed. It may be a copolymer obtained by copolymerizing another copolymerizable ethylenically unsaturated monomer.
  • the conjugated diene-based polymer used in the present invention may be an acid-modified conjugated diene-based polymer obtained by modifying with a monomer having an acidic group, or a carboxy-modified carboxy-modified conjugated diene-based polymer. Is preferable.
  • the carboxy-modified conjugated diene-based polymer can be obtained by modifying the above-mentioned conjugated diene-based polymer with a monomer having a carboxyl group.
  • an ethylenically unsaturated carboxylic acid monomer is used as the other possible ethylenically unsaturated monomer as the nitrile group-containing conjugated diene copolymer, it has already been carboxy-modified. Modification with a monomer having a carboxyl group, which will be described later, is not always necessary.
  • the method for modifying the conjugated diene polymer with a monomer having a carboxyl group is not particularly limited, but for example, a monomer having a carboxyl group is graft-polymerized on the conjugated diene polymer in an aqueous phase.
  • the method can be mentioned.
  • the method for graft-polymerizing a monomer having a carboxyl group in the conjugated diene polymer in the aqueous phase is not particularly limited, and a conventionally known method may be used. For example, in the latex of the conjugated diene polymer.
  • a method in which a monomer having a carboxyl group and a graft polymerization catalyst are added and then the conjugated diene polymer is reacted with the monomer having a carboxyl group in an aqueous phase is preferable.
  • the graft polymerization catalyst is not particularly limited, and for example, inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide; diisopropylbenzene hydroperoxide, cumene hydroperoxide, etc.
  • inorganic peroxides such as sodium persulfate, potassium persulfate, ammonium persulfate, potassium perphosphate, and hydrogen peroxide
  • diisopropylbenzene hydroperoxide diisopropylbenzene hydroperoxide, cumene hydroperoxide, etc.
  • Organic peroxides such as t-butyl hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, di-t-butyl peroxide, isobutyryl peroxide, benzoyl peroxide; 2,2'- Azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azo compounds such as methyl azobisisobutyrate; and the like; From this point of view, organic peroxide is preferable, and 1,1,3,3-tetramethylbutylhydroperoxide is particularly preferable.
  • These graft polymerization catalysts may be used alone or in combination of two or more.
  • the above graft polymerization catalysts can be used alone or in combination of two or more.
  • the amount of the graft polymerization catalyst used varies depending on the type, but is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of the conjugated diene polymer.
  • the method for adding the graft polymerization catalyst is not particularly limited, and known addition methods such as batch addition, divided addition, and continuous addition can be adopted.
  • the organic peroxide can be used as a redox-based polymerization initiator in combination with a reducing agent.
  • the reducing agent is not particularly limited, but for example, a compound containing a metal ion in a reduced state such as ferrous sulfate and ferrous naphthenate; a sulfinate such as sodium hydroxymethanesulfinate; a dimethylaniline and the like. Amine compounds; etc. These reducing agents may be used alone or in combination of two or more.
  • the amount of the reducing agent added is not particularly limited, but is preferably 0.01 to 1 part by weight with respect to 1 part by weight of the organic peroxide.
  • the method for adding the organic peroxide is not particularly limited, and known addition methods such as batch addition, divided addition, and continuous addition can be used, respectively.
  • the reaction temperature when reacting the conjugated diene polymer with the monomer having a carboxyl group is not particularly limited, but is preferably 15 to 80 ° C, more preferably 30 to 50 ° C.
  • the reaction time for reacting the conjugated diene polymer with the monomer having a carboxyl group may be appropriately set according to the above reaction temperature, but is preferably 30 to 300 minutes, more preferably 60 to 120 minutes. is there.
  • the solid content concentration of the latex of the conjugated diene polymer in reacting the conjugated diene polymer with a monomer having a carboxyl group is not particularly limited, but is preferably 5 to 60% by weight, more preferably 10 to 10 to 60% by weight. It is 40% by weight.
  • Examples of the monomer having a carboxyl group include ethylenically unsaturated monocarboxylic acid monomers such as acrylic acid and methacrylic acid; and ethylenically unsaturated polyvalents such as itaconic acid, maleic acid, fumaric acid, and butentricarboxylic acid.
  • ethylenically unsaturated monocarboxylic acid monomers such as acrylic acid and methacrylic acid
  • ethylenically unsaturated polyvalents such as itaconic acid, maleic acid, fumaric acid, and butentricarboxylic acid.
  • Carboxylic acid monomer Partial ester monomer of ethylenically unsaturated polyvalent carboxylic acid such as monobutyl fumarate, monobutyl maleate, mono2-hydroxypropyl maleate; polyvalent carboxylic acid such as maleic anhydride and citraconic anhydride Acid anhydrides; and the like can be mentioned, but ethylenically unsaturated monocarboxylic acid monomers are preferable, and acrylic acid and methacrylic acid are particularly preferable, because the effect of carboxy modification becomes even more remarkable. It should be noted that these monomers may be used alone or in combination of two or more. Further, the above-mentioned carboxyl group includes those which are salts with alkali metals, ammonia and the like.
  • the amount of the monomer having a carboxyl group to be used is preferably 0.01 parts by weight to 100 parts by weight, more preferably 0.01 parts by weight to 40 parts by weight, and further, with respect to 100 parts by weight of the conjugated diene polymer. It is preferably 0.5 parts by weight to 20 parts by weight.
  • the method of adding the monomer having a carboxyl group to the latex of the conjugated diene polymer is not particularly limited, and known addition methods such as batch addition, divided addition, and continuous addition can be adopted.
  • the modification rate of the carboxy-modified conjugated diene-based polymer by the monomer having a carboxyl group may be appropriately controlled according to the intended use of the obtained conjugated diene-based polymer latex composition, but is preferably 0.01 to 10. It is% by weight, more preferably 0.2 to 5% by weight, still more preferably 0.3 to 3% by weight, and particularly preferably 0.4 to 2% by weight.
  • the denaturation rate is expressed by the following formula.
  • Degeneration rate (% by weight) (X / Y) x 100
  • X represents the weight of the unit of the monomer having a carboxyl group in the carboxy-modified conjugated diene-based polymer
  • Y represents the weight of the carboxy-modified conjugated diene-based polymer.
  • X is calculated from a method of performing 1 H-NMR measurement on a carboxy-modified conjugated diene polymer and calculating from the result of 1 H-NMR measurement, or obtaining an acid amount by neutralization titration and calculating from the obtained acid amount. It can be obtained by a method or the like.
  • the latex of the conjugated diene polymer (including the acid-modified conjugated diene polymer) used in the present invention contains a pH adjuster, an antifoaming agent, an antiseptic, and a chelating agent, which are usually blended in the field of latex. , Oxygen trapping agent, dispersant, antiaging agent and other additives may be blended.
  • Examples of the pH adjuster include hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal bicarbonates such as sodium hydrogen carbonate; ammonia. ; Organic amine compounds such as trimethylamine and triethanolamine; etc., but alkali metal hydroxides or ammonia are preferable.
  • the solid content concentration of the latex of the conjugated diene polymer (including the acid-modified conjugated diene polymer) used in the present invention is preferably 30 to 70% by weight, more preferably 40 to 70% by weight.
  • the conjugated diene polymer latex composition of the present invention contains the above-mentioned xanthogen compound dispersion of the present invention and a vulcanizing agent in addition to the above-mentioned latex of the conjugated diene polymer.
  • the blending amount of the xanthogen compound dispersion in the conjugated diene polymer latex composition of the present invention is not particularly limited, but the content of the xanthogen compound with respect to 100 parts by weight of the conjugated diene polymer is preferably 0.01.
  • the amount is up to 10 parts by weight, more preferably 0.1 to 7 parts by weight, and even more preferably 0.5 to 5 parts by weight.
  • the xanthogen compound contained in the xanthogen compound dispersion exists in the form of a xanthate salt due to the action of the activator contained in the conjugated diene polymer latex composition of the present invention, and as a result, it is conjugated.
  • Two or more kinds of xanthogen compounds may be contained in the diene polymer latex composition.
  • the conjugated diene polymer latex composition contains sulfur as a sulfur-based vulcanizing agent or the like, a part of the xanthogen compound is contained in the conjugated diene polymer latex composition due to the action of sulfur.
  • Xantogen disulfide or xanthogen polysulfide may be present in the form.
  • a sulfur-based vulcanizing agent is preferably used.
  • the sulfur-based sulfurizing agent include sulfur powder, sulfur flower, precipitated sulfur, colloidal sulfur, surface-treated sulfur, and insoluble sulfur; sulfur chloride, sulfur dichloride, morpholin disulfide, alkylphenol disulfide, and caprolactam disulfide (N). , N'-dithio-bis (hexahydro-2H-azepinone-2)), phosphorus-containing polysulfide, high molecular weight polysulfide, 2- (4'-morpholinodithio) benzothiazole and other sulfur-containing compounds.
  • sulfur can be preferably used.
  • the sulfur-based vulcanizing agent may be used alone or in combination of two or more.
  • the content of the vulcanizing agent in the latex composition of the present invention is not particularly limited, but is preferably 0.1 to 10 parts by weight, more preferably 0.2 parts by weight, based on 100 parts by weight of the conjugated diene polymer. It is up to 5 parts by weight, more preferably 0.5 to 3 parts by weight.
  • the conjugated diene polymer latex composition of the present invention preferably further contains a metal oxide and / or a typical metal compound, and more preferably at least a metal oxide.
  • the metal oxide and the main group metal compound act as an activator when used together with the xanthate compound contained in the xanthate compound dispersion. Further, the metal oxide and the typical metal compound also act as a cross-linking agent for cross-linking an acidic group when an acid-modified conjugated diene-based polymer is used as the conjugated diene-based polymer, whereby a dip molded product obtained by the above. It is possible to further increase the tensile strength and tear strength of the film-molded article such as.
  • the metal oxide is not particularly limited, but includes zinc oxide, magnesium oxide, titanium oxide, calcium oxide, lead oxide, iron oxide, copper oxide, tin oxide, nickel oxide, chromium oxide, cobalt oxide, and aluminum oxide. Can be mentioned. Among these, zinc oxide is preferable from the viewpoint of further improving the tensile strength and tear strength of the obtained film molded product such as a dip molded product. These metal oxides may be used alone or in combination of two or more.
  • the typical metal compound may be a typical metal compound other than an oxide, and is not particularly limited, but is not particularly limited, but is a typical metal hydroxide, carbon oxide, sulfate, glass oxide, phosphor oxide, chloride, bromide, or iodide. Of these, carbon oxides, which are typical metals, are preferable.
  • typical metal compounds include compounds such as zinc, magnesium, calcium, lead, tin, and aluminum, and among them, zinc compounds are preferable. Among these, zinc carbonate is preferable from the viewpoint of further improving the tensile strength and tear strength of the obtained film molded product such as a dip molded product. These typical metal compounds may be used alone or in combination of two or more.
  • the total content of the metal oxide and / or the typical metal compound in the conjugated diene polymer latex composition of the present invention is not particularly limited, but is preferably 0 with respect to 100 parts by weight of the conjugated diene polymer. It is 0.01 to 30 parts by weight, more preferably 0.1 to 10 parts by weight, still more preferably 0.5 to 5 parts by weight.
  • the conjugated diene polymer latex composition of the present invention is further provided with a xanthogen compound as long as it can suppress the occurrence of delayed type allergy (Type IV) symptoms in the obtained film molded product such as a dip molded product.
  • a vulcanization accelerator other than the above may be contained.
  • the content of the vulcanization accelerator other than the xanthate compound is preferably 20% by weight or less, preferably 10% by weight, based on the total content of the xanthate compound and the vulcanization accelerator other than the xanthate compound. It is more preferably 0% by weight (that is, it does not contain a vulcanization accelerator other than the xanthate compound).
  • sulfide accelerator other than the xanthogen compound those usually used in film molding such as dip molding can be used, and for example, diethyldithiocarbamic acid, dibutyldithiocarbamic acid, di-2-ethylhexyldithiocarbamic acid, dicyclohexyldithiocarbamic acid, diphenyldithiocarbamine.
  • Dithiocarbamic acids such as acids, dibenzyldithiocarbamic acid and their zinc salts; 2-mercaptobenzothiazole, 2-mercaptobenzothiazole zinc, 2-mercaptothiazolin, dibenzothiazyl disulfide, 2- (2,4-dinitrophenylthio) ) Benzothiazole, 2- (N, N-diethylthio carbamoylthio) benzothiazole, 2- (2,6-dimethyl-4-morpholinothio) benzothiazole, 2- (4'-morpholino dithio) benzothiazole, 4 -Morphorinyl-2-benzothiazyl disulfide, 1,3-bis (2-benzothiazyl mercaptomethyl) urea and the like can be mentioned.
  • vulcanization accelerators other than thiuram-based vulcanization accelerators, dithiocarbamate-based vulcanization accelerators, and thiazole-based vulcanization accelerators are preferable to use.
  • the vulcanization accelerator other than the xanthate compound can be used alone or in combination of two or more.
  • the conjugated diene polymer latex composition of the present invention further includes an antiaging agent; a dispersant; a reinforcing agent such as carbon black, silica and talc; a filler such as calcium carbonate and clay; an ultraviolet absorber; a plasticizer; Etc. can be blended as needed.
  • Anti-aging agents include 2,6-di-4-methylphenol, 2,6-di-t-butylphenol, butylhydroxyanisole, 2,6-di-t-butyl- ⁇ -dimethylamino-p-cresol, Octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, styrenated phenol, 2,2'-methylene-bis (6- ⁇ -methyl-benzyl-p-cresol), 4, Butylation of 4'-methylenebis (2,6-di-t-butylphenol), 2,2'-methylene-bis (4-methyl-6-t-butylphenol), alkylated bisphenol, p-cresol and dicyclopentadiene Phenolic antioxidants that do not contain sulfur atoms such as reaction products; 2,2'-thiobis- (4-methyl-6-t-butylphenol), 4,4'-thiobis- (6-t-butyl-) O-cresol), 2,6-d
  • the content of the antioxidant in the conjugated diene polymer latex composition of the present invention is preferably 0.05 to 10 parts by weight, more preferably 0, based on 100 parts by weight of the carboxy-modified conjugated diene polymer. .1 to 5 parts by weight.
  • the method for preparing the conjugated diene polymer latex composition of the present invention is not particularly limited, but for example, the latex of the conjugated diene polymer described above, a vulcanizing agent, a xanthogen compound dispersion, and if necessary. Examples thereof include a method of mixing various compounding agents used in the above. In this case, a method of preparing an aqueous dispersion of a compounding component other than the latex of the conjugated diene polymer and then mixing the aqueous dispersion with the latex of the conjugated diene polymer can also be adopted.
  • the solid content concentration of the conjugated diene polymer latex composition of the present invention is preferably 10 to 60% by weight, more preferably 10 to 55% by weight.
  • the conjugated diene-based polymer of the present invention may be prepared before being subjected to film-molding such as dip molding.
  • the latex composition is preferably aged (pre-vulcanized).
  • the aging (pre-vulcanization) time is not particularly limited, but is preferably 8 to 120 hours, more preferably 24-72 hours.
  • the temperature of aging (pre-vulcanization) is not particularly limited, but is preferably 20 to 40 ° C.
  • the conjugated diene polymer latex composition of the present invention when using the conjugated diene polymer latex composition of the present invention, after aging (pre-vulcanization) for a predetermined time, the aging (pre-vulcanization) conditions are maintained (aging (pre-vulcanization)). ), Film molding such as dip molding may be continuously performed, and the aging (pre-vulcanization) time and aging (pre-vulcanization) temperature in this case may be within the above ranges.
  • the conjugated diene polymer latex composition of the present invention contains the above-mentioned xanthogen compound dispersion of the present invention, the tensile strength even when the aging (pre-vulcanization) time is relatively long as described above.
  • the film-molded article of the present invention is a film-shaped molded article composed of the above-mentioned conjugated diene-based polymer latex composition of the present invention.
  • the film thickness of the film molded product of the present invention is preferably 0.03 to 0.50 mm, more preferably 0.05 to 0.40 mm, and particularly preferably 0.08 to 0.30 mm.
  • the film molded product of the present invention is not particularly limited, but a dip molded product obtained by dip molding the conjugated diene polymer latex composition of the present invention is preferable.
  • Dip molding involves immersing a mold in a conjugated diene polymer latex composition, depositing the composition on the surface of the mold, then pulling the mold out of the composition, and then depositing the composition on the surface of the mold. Is a method of drying.
  • the mold before being immersed in the conjugated diene polymer latex composition may be preheated. Further, a coagulant can be used as needed before immersing the mold in the conjugated diene polymer latex composition or after pulling the mold out of the conjugated diene polymer latex composition.
  • the method of using the coagulant include a method of immersing the mold before being immersed in the conjugated diene polymer latex composition in a solution of the coagulant to attach the coagulant to the mold (anode adhesion immersion method).
  • anode adhesion immersion method There is a method of immersing a mold in which a conjugated diene polymer latex composition is deposited in a coagulant solution (Teeg adhesion immersion method), but it is possible to obtain a dip molded body with less uneven thickness, so that it is immersed in an anode adhesion. The method is preferred.
  • the coagulant include metal halides such as barium chloride, calcium chloride, magnesium chloride, zinc chloride and aluminum chloride; nitrates such as barium nitrate, calcium nitrate and zinc nitrate; acetic acid such as barium acetate, calcium acetate and zinc acetate. Salts; water-soluble polyvalent metal salts such as calcium sulfate, magnesium sulfate, sulfates such as aluminum sulfate; Of these, calcium salts are preferable, and calcium nitrate is more preferable. These water-soluble polyvalent metal salts can be used alone or in combination of two or more.
  • the coagulant can usually be used as a solution of water, alcohol, or a mixture thereof, and is preferably used in the state of an aqueous solution.
  • This aqueous solution may further contain a water-soluble organic solvent such as methanol or ethanol or a nonionic surfactant.
  • the concentration of the coagulant varies depending on the type of the water-soluble polyvalent metal salt, but is preferably 5 to 50% by weight, more preferably 10 to 30% by weight.
  • the mold After the mold is pulled up from the conjugated diene polymer latex composition, it is usually heated to dry the deposits formed on the mold.
  • the drying conditions may be appropriately selected.
  • the obtained dip molded layer is heat-treated and vulcanized.
  • the mixture before the heat treatment, the mixture is immersed in water, preferably warm water at 30 to 70 ° C. for about 1 to 60 minutes to remove water-soluble impurities (for example, excess emulsifier, coagulant, etc.). You may.
  • the operation for removing water-soluble impurities may be performed after the dip molding layer has been heat-treated, but it is preferably performed before the heat treatment because the water-soluble impurities can be removed more efficiently.
  • Vulcanization of the dip molded layer is usually carried out by heat treatment at a temperature of 80 to 150 ° C., preferably for 10 to 130 minutes.
  • a method of external heating by infrared rays or heated air or internal heating by high frequency can be adopted. Of these, external heating with heated air is preferable.
  • the dip molded body can be obtained as a film-shaped film molded body.
  • a desorption method a method of manually peeling from the molding mold or a method of peeling by water pressure or compressed air pressure can be adopted. After desorption, heat treatment may be further performed at a temperature of 60 to 120 ° C. for 10 to 120 minutes.
  • the film-molded product of the present invention is a film-like conjugated diene-based polymer latex composition of the present invention described above. Any method may be used as long as it can be molded into (for example, a coating method).
  • the film molded product of the present invention can suppress the occurrence of symptoms of delayed type allergy (Type IV) in addition to immediate type allergy (Type I), and also has tensile strength and tear strength. It is excellent in stability of tensile strength and tear strength, and can be particularly preferably used as a glove, for example.
  • gloves are made of inorganic fine particles such as talc and calcium carbonate or organic fine particles such as starch particles. It may be sprayed on the surface, an elastomer layer containing fine particles may be formed on the surface of the glove, or the surface layer of the glove may be chlorinated.
  • the film molded product of the present invention including the dip molded product of the present invention includes medical supplies such as baby bottle nipples, droppers, tubes, water pillows, balloon sack, catheters, condoms; balloons, dolls, etc. , Balls and other toys; industrial products such as pressure molding bags and gas storage bags; can also be used for finger cots and the like.
  • the above-mentioned conjugated diene polymer latex composition of the present invention can be used as the adhesive composition.
  • the content (solid content) of the conjugated diene-based polymer latex composition of the present invention in the adhesive composition is preferably 5 to 60% by weight, more preferably 10 to 30% by weight.
  • the adhesive composition preferably contains an adhesive resin in addition to the conjugated diene polymer latex composition of the present invention.
  • the adhesive resin is not particularly limited, but for example, resorcin-formaldehyde resin, melamine resin, epoxy resin and isocyanate resin can be preferably used, and among these, resorcin-formaldehyde resin is preferable.
  • resorcin-formaldehyde resin known ones (for example, those disclosed in JP-A-55-142635) can be used.
  • the reaction ratio of resorcin to formaldehyde is a molar ratio of "resorcin: formaldehyde", usually 1: 1 to 1: 5, preferably 1: 1 to 1: 3.
  • the adhesive composition contains 2,6-bis (2,4-dihydroxyphenylmethyl) -4-chlorophenol or the like conventionally used.
  • Compounds, isocyanates, blocked isocyanates, ethylene ureas, polyepoxides, modified polyvinyl chloride resins and the like can be contained.
  • the adhesive composition can contain a cross-linking aid.
  • a cross-linking aid By containing the cross-linking aid, the mechanical strength of the complex described later obtained by using the adhesive composition can be improved.
  • the cross-linking aid include quinone dioximes such as p-quinone dioxime; methacrylate esters such as lauryl methacrylate and methyl methacrylate; DAF (diallyl fumarate), DAP (diallyl phthalate), TAC (triallyl cyanurate), and TAIC. Allyl compounds such as (triallyl isocyanurate); maleimide compounds such as bismaleimide, phenylmaleimide, N, Nm-phenylenedi maleimide; sulfur; and the like can be mentioned.
  • ⁇ Modification rate of carboxy-modified synthetic polyisoprene> The number of carboxyl groups in the carboxy-modified synthetic polyisoprene was determined by neutralization titration using an aqueous sodium hydroxide solution for the carboxy-modified synthetic polyisoprene constituting the latex of the carboxy-modified synthetic polyisoprene. Then, based on the obtained number of carboxyl groups, the modification rate of the monomer having a carboxyl group was determined according to the following formula.
  • Degeneration rate (% by weight) (X / Y) x 100
  • X represents the weight of the unit of the monomer having a carboxyl group in the carboxy-modified synthetic polyisoprene
  • Y represents the weight of the carboxy-modified synthetic polyisoprene
  • ⁇ Number average molecular weight (Mn) of nonionic surfactant> A nonionic surfactant was dissolved in tetrahydrofuran to prepare a 0.2 wt% solution, and then filtered through a 0.45 ⁇ m membrane filter as a measurement sample, which was subjected to gel permeation chromatography (GPC) under the following conditions. The number average molecular weight (Mn) of the nonionic surfactant in terms of standard polystyrene was determined by the measurement.
  • Measuring device HLC-8220GPC (manufactured by Tosoh) Column: TSKgel G1000H (manufactured by Tosoh), TSKgel G2000H (manufactured by Tosoh) Eluent: tetrahydrofuran (THF) Elution rate: 0.3 ml / min Detector: RI (polarity (+)) Column temperature: 40 ° C
  • the measurement was performed on 5 test pieces, and the tensile strength of the test piece showing the median value among the measured values of the 5 test pieces (that is, the third largest value among the 5 test pieces). Value) was adopted as the value of tensile strength. It can be judged that the higher the tensile strength, the better the tensile strength. Further, it can be judged that the smaller the difference between the tensile strength of the 24-hour aged product and the tensile strength of the 72-hour aged product, the better the stability of the tensile strength.
  • the measurement was performed on 5 test pieces, and the tear strength of the test piece showing the median value among the measured values of the 5 test pieces (that is, the third largest value among the 5 test pieces). Value) was adopted as the value of tear strength. It can be judged that the higher the tear strength, the better the tear strength. Further, it can be judged that the smaller the difference between the tear strength of the 24-hour aged product and the tear strength of the 72-hour aged product, the better the stability of the tear strength.
  • ⁇ Manufacturing example 1> (Manufacture of latex of carboxy-modified synthetic polyisoprene) Synthetic polyisoprene having a weight average molecular weight of 1,300,000 (trade name "NIPOL IR2200L", manufactured by Nippon Zeon Co., Ltd., isoprene homopolymer, cis bond unit amount 98%) is mixed with cyclohexane and heated while stirring. Was dissolved by raising the temperature to 60 ° C. to prepare a cyclohexane solution (a) of synthetic polyisoprene having a viscosity of 12,000 mPa ⁇ s measured by a B-type viscosity meter (solid content concentration: 8% by weight).
  • an aqueous anionic surfactant solution (b) having a concentration of 1.5% by weight 20 parts of sodium rosinate was added to water, the temperature was raised to 60 ° C. and dissolved to prepare an aqueous anionic surfactant solution (b) having a concentration of 1.5% by weight.
  • the cyclohexane solution (a) and the anionic surfactant aqueous solution (b) are mixed in a mixer (trade name “Multiline Mixer MS26-MMR-5” so as to have a weight ratio of 1: 1.5. .5L ”, manufactured by Satake Kagaku Kikai Kogyo Co., Ltd.), and then mixed and emulsified using an emulsifying device (trade name“ Milder MDN310 ”, manufactured by Pacific Kiko Co., Ltd.) at a rotation speed of 4100 rpm to emulsify. Liquid (c) was obtained.
  • a mixer trade name “Multiline Mixer MS26-MMR-5” so as to have a weight ratio of 1: 1.5. .5L ”, manufactured by Satake Kagaku Kikai Kogyo Co., Ltd.
  • an emulsifying device trade name“ Milder MDN310 ”, manufactured by Pacific Kiko Co., Ltd.
  • the total feed flow velocity of the cyclohexane solution (a) and the anionic surfactant aqueous solution (b) was 2,000 kg / hr, the temperature was 60 ° C., and the back pressure (gauge pressure) was 0.5 MPa.
  • the emulsion (c) was heated to 80 ° C. under a reduced pressure of ⁇ 0.01 to ⁇ 0.09 MPa (gauge pressure), cyclohexane was distilled off, and an aqueous dispersion (d) of synthetic polyisoprene was added. Obtained.
  • an antifoaming agent (trade name "SM5515", manufactured by Toray Dow Corning Co., Ltd.) was continuously added while spraying so as to have an amount of 300 ppm by weight based on the synthetic polyisoprene in the emulsion (c). ..
  • the emulsion (c) When distilling off cyclohexane, the emulsion (c) is adjusted to be 70% by volume or less of the volume of the tank, and a three-stage inclined paddle blade is used as the stirring blade, and the mixture is slowly stirred at 60 rpm. Was carried out.
  • the obtained aqueous dispersion (d) of synthetic polyisoprene is used in a continuous centrifuge (trade name "SRG510", manufactured by Alfa Laval) from 4,000 to Centrifugation at 5,000 G gave a latex (e) of synthetic polyisoprene as a light liquid.
  • the conditions for centrifugation are as follows: the solid content concentration of the aqueous dispersion (d) before centrifugation is 10% by weight, the flow velocity during continuous centrifugation is 1300 kg / hr, and the back pressure (gauge pressure) of the centrifuge is 1. It was set to 5 MPa.
  • the obtained synthetic polyisoprene latex (e) had a solid content concentration of 60% by weight.
  • the latex (e) of synthetic polyisoprene to which a dispersant was added was charged into a reaction vessel equipped with a stirrer substituted with nitrogen, and the temperature was heated to 30 ° C. while stirring. Further, using another container, 3 parts of methacrylic acid as a monomer having a carboxyl group and 16 parts of distilled water were mixed to prepare a diluted methacrylic acid solution. This diluted methacrylic acid solution was added to a reaction vessel heated to 30 ° C. over 30 minutes.
  • the carboxy-modified synthetic polyisoprene was concentrated with a centrifuge to obtain a light liquid having a solid content concentration of 55%. Then, with respect to the obtained latex of the carboxy-modified synthetic polyisoprene, the modification rate of the obtained monomer having a carboxyl group was measured according to the above method, and the modification rate was 0.5% by weight.
  • ⁇ Manufacturing example 2> Manufacturing of SIS latex
  • SIS trade name "Quintac 3620", manufactured by Nippon Zeon Co., Ltd.
  • the solid content concentration of the obtained SIS latex was 60% by weight.
  • Example 1> (Preparation of xanthate compound dispersion) Zinc diisopropylxanthogenate as a xanthogen compound (trade name "Noxeller ZIX”, manufactured by Ouchi Shinko Kagaku Kogyo Co., Ltd., volume average particle size: 14 ⁇ m, 95% volume cumulative diameter (D95): 55 ⁇ m) 2.5 parts, polyoxy Sodium salt of ⁇ -naphthalene sulfonic acid formalin condensate as an anionic surfactant having no alkylene structure (trade name "Demor T-45”, manufactured by Kao, weight average molecular weight: 7,000) 0.22 parts, 0.06 parts of polyoxyethylene oleyl ether as a nonionic surfactant (trade name "Emargen 404", manufactured by Kao, number average molecular weight (Mn): 421), and 4.5 parts of water, ball mill (trade name) A xanthate compound dispersion was obtained by crushing by mixing with a "Noxeller
  • a styrene-maleic acid mono-sec-butyl ester-maleic acid monomethyl ester polymer (trade name "Scripest550", manufactured by Hercules) was prepared, and sodium hydroxide was used to contain 100% of the carboxyl groups in the polymer.
  • an aqueous sodium salt solution (concentration: 10% by weight) was prepared.
  • this aqueous sodium salt solution was added to the latex of the carboxy-modified synthetic polyisoprene obtained in Production Example 1 so that the solid content was 0.8 parts with respect to 100 parts of the carboxy-modified synthetic polyisoprene in the latex. Addition gave a mixture.
  • the aqueous dispersion of each compounding agent was added so as to have 1.5 parts of zinc oxide, 1.5 parts of sulfur, and 2 parts of an antiaging agent (trade name "Wingstay L", manufactured by Goodyear Tire and Rubber Co., Ltd.) in terms of solid content. Addition gave a latex composition. Then, the obtained latex composition was divided into two, one of which was aged for 24 hours (pre-vulcanization) in a constant temperature water bath adjusted to 25 ° C., and the other was a constant temperature water tank adjusted to 25 ° C. By carrying out aging (pre-vulcanization) for 72 hours in the above, a 24-hour aged latex composition and a 72-hour aged latex composition were obtained.
  • the hand mold coated with the coagulant was taken out from the oven and immersed in the 24-hour aged latex composition obtained above for 10 seconds.
  • the hand mold was air-dried at room temperature for 10 minutes and then immersed in warm water at 60 ° C. for 5 minutes to elute water-soluble impurities to form a dip molding layer on the hand mold.
  • the dip-molded layer formed in the hand mold is vulcanized by heating it in an oven at a temperature of 130 ° C. for 30 minutes, cooled to room temperature, sprayed with talc, and then peeled off from the hand mold.
  • a glove-shaped dip molded product (aged for 24 hours) was obtained.
  • a glove-shaped dip molded product (72-hour aged product) was obtained in the same manner as above except that the 72-hour aged latex composition was used instead of the 24-hour aged latex composition. Then, using the obtained dip molded products (24-hour aged product and 72-hour aged product), the tensile strength and the tear strength were measured according to the above method. The results are shown in Table 1.
  • Example 2 Xanthogen compound dispersion in the same manner as in Example 1 except that the amount of the sodium salt of the ⁇ -naphthalene sulfonic acid formalin condensate was 0.14 parts and the amount of the polyoxyethylene oleyl ether was 0.14 parts. I got a body.
  • the volume average particle size and the 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained dispersion of the xanthogen compound were measured in the same manner as in Example 1, the volume average particle size of zinc diisopropylxanthogenate was found. It was 2.3 ⁇ m, and the 95% cumulative volume diameter (D95) was 3.9 ⁇ m.
  • Example 1 a 24-hour aged latex composition, a 72-hour aged latex composition, and a dip molded product (24-hour aged product and 72-hour aged product) were used, except that the obtained xanthogen compound dispersion was used. Aged product) was obtained and measured in the same manner. The results are shown in Table 1.
  • Example 3 Xanthogen compound dispersion in the same manner as in Example 1 except that the amount of the sodium salt of the ⁇ -naphthalene sulfonic acid formalin condensate was 0.06 part and the amount of the polyoxyethylene oleyl ether was 0.22 part. I got a body.
  • the volume average particle size and the 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained dispersion of the xanthogen compound were measured in the same manner as in Example 1, the volume average particle size of zinc diisopropylxanthogenate was found. It was 2.8 ⁇ m, and the 95% cumulative volume diameter (D95) was 4.4 ⁇ m.
  • Example 1 a 24-hour aged latex composition, a 72-hour aged latex composition, and a dip molded product (24-hour aged product and 72-hour aged product) were used, except that the obtained xanthogen compound dispersion was used. Aged product) was obtained and measured in the same manner. The results are shown in Table 1.
  • Example 4 Except for using 0.06 parts of polyoxyethylene octyldodecyl ether (trade name "Emargen 2025G", manufactured by Kao Corporation, number average molecular weight (Mn): 2450) instead of 0.06 parts of polyoxyethylene oleyl ether.
  • a xanthogen compound dispersion was obtained in the same manner as in Example 1.
  • the volume average particle size and the 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained dispersion of the xanthogen compound were measured in the same manner as in Example 1, the volume average particle size of zinc diisopropylxanthogenate was found.
  • Example 5 The 24-hour aged latex composition and the latex aged in the same manner as in Example 4 except that the latex of SIS obtained in Production Example 2 was used instead of the latex of the carboxy-modified synthetic polyisoprene obtained in Production Example 1.
  • a 72-hour aged latex composition and a dip molded product were obtained and measured in the same manner. The results are shown in Table 1.
  • ⁇ Comparative example 1> A xanthogen compound dispersion was obtained in the same manner as in Example 1 except that the sodium salt of the ⁇ -naphthalene sulfonic acid formalin condensate was used in an amount of 0.28 parts and polyoxyethylene oleyl ether was not used.
  • the volume average particle size and the 95% volume cumulative diameter (D95) of zinc diisopropylxanthogenate in the obtained xanthogen compound dispersion were measured in the same manner as in Example 1, the volume average particle size of zinc diisopropylxanthogenate was found. It was 2.1 ⁇ m and the 95% cumulative volume diameter (D95) was 3.8 ⁇ m.
  • Example 1 a 24-hour aged latex composition, a 72-hour aged latex composition, and a dip molded product (24-hour aged product and 72-hour aged product) were used, except that the obtained xanthogen compound dispersion was used. Aged product) was obtained and measured in the same manner. The results are shown in Table 1.
  • a xanthate compound dispersion containing a xanthogen compound, an anionic surfactant having no polyoxyalkylene structure, a nonionic surfactant, and water or alcohol is used as a vulcanization accelerator.
  • a vulcanization accelerator for example, thiuram-based vulcanization accelerator, dithiocarbamate-based vulcanization accelerator, thiazole-based vulcanization accelerator, etc.
  • a vulcanized product could be obtained without use, and it was possible to suppress the occurrence of symptoms of delayed type allergy (Type IV) in addition to immediate type allergy (Type I).
  • the obtained dip molded product was excellent in tensile strength and tear strength, and was also excellent in stability of tensile strength and tear strength. Further, according to the above-mentioned xanthogen compound dispersion, the obtained latex composition is aged for 24 hours before the production of the dip molded product is started, and the production of the dip molded product is continued for 48 hours or more while maintaining the aging conditions. Even when the above was continuously performed, it was possible to stably produce a dip molded product having excellent tensile strength and tear strength. That is, the obtained latex composition was excellent in aging stability (Examples 1 to 5).

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  • Organic Chemistry (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
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Abstract

L'invention fournit une dispersion de composé xanthogène qui comprend : un composé xanthogène ; un tensio-actif anionique exempt de structure polyoxyalkylène ; un tensio-actif non ionique ; et une eau ou un alcool.
PCT/JP2020/047421 2019-12-27 2020-12-18 Dispersion de composé xanthogène, composition de latex de polymère à base de diène conjugué, corps moulé de film, corps moulé par immersion, et composition d'adhésif WO2021132075A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012158694A (ja) * 2011-02-01 2012-08-23 Denki Kagaku Kogyo Kk 水系接着剤組成物及びウェットスーツ素材の製造方法
WO2018143159A1 (fr) * 2017-02-01 2018-08-09 デンカ株式会社 Composition de latex polymère à base de chloroprène, composition de latex mixte l'utilisant et utilisation associée
WO2018155243A1 (fr) * 2017-02-22 2018-08-30 日本ゼオン株式会社 Composition de latex
WO2019003744A1 (fr) * 2017-06-30 2019-01-03 日本ゼオン株式会社 Corps moulé sous forme de film
WO2020054248A1 (fr) * 2018-09-14 2020-03-19 日本ゼオン株式会社 Dispersion de composé xanthogène, composition de latex polymère à base de diène conjugué et corps moulé en film

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2012158694A (ja) * 2011-02-01 2012-08-23 Denki Kagaku Kogyo Kk 水系接着剤組成物及びウェットスーツ素材の製造方法
WO2018143159A1 (fr) * 2017-02-01 2018-08-09 デンカ株式会社 Composition de latex polymère à base de chloroprène, composition de latex mixte l'utilisant et utilisation associée
WO2018155243A1 (fr) * 2017-02-22 2018-08-30 日本ゼオン株式会社 Composition de latex
WO2019003744A1 (fr) * 2017-06-30 2019-01-03 日本ゼオン株式会社 Corps moulé sous forme de film
WO2020054248A1 (fr) * 2018-09-14 2020-03-19 日本ゼオン株式会社 Dispersion de composé xanthogène, composition de latex polymère à base de diène conjugué et corps moulé en film

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